Dyestuffs of the stilbene series and a process of making same



Patented Feb. 6, 1945 UNITED} j STATES PATENT OFFICE.

. DYESTUFFS OF THE STILBENE SERIES AND f A PROCESS OF MAKING SAME Ernst Keller and Reinhard Zweidler, Basel,

Switzerland,

assignorsto the firm J. R.

Geigy A. G., Basel, Switzerland No Drawing. Application February 15,, 1944, serial No. 522,500; In SwitzerlandFebruary 10,

We 'have found that new dyestuffs of the stil bene series are obtained byconverting condensation products of cyanuric halides, in which a halogen atom of the cyanuric halide is replaced by the radical'of the 4-nitro4'-aminostilbene-2:2'-di sulfonic acid and in which the remaining halogenatoms of the cyanuric' nucleus may be exchanged completely or partly by inorganic or organicradicals, especially by radicals of amines, Which may also contain azo groups, by way of reduction into azo or azoxy compounds. The conversion of the fi-positioned nitro group into an azo or azoxy group respectively is carried out in a known'mannor by, reduction in an alkaline solution for instance by means of glucose, sodium sulfide and the .like. The dyestuffs .thus' obtained may still be after-treated with oxidation agents, as this is knownforstilbenedyestuffs.

The condensation products with cyanuric halide coming into question correspond to the following general formula:

In this formula X1 and X2 mean the sameor different organic or polyatomic inorganic radicals.

' As radicals X1 and X2 which stand in the place of two halogen atoms'of the cyanuric ring there may be mentioned the following which may be subdivided into groups in accordance with their properties:

(a) Radicals capable of ,forming azo dyestufis directly or after their corresponding conversion, inc; -radicals containingdiazotisableamino groups or substituents allowing the coupling with suitable diazo components. substituents enabling the formation, of azo dyestufis are for instance: aromatically,boundaminogroupsi of the general formula NR1'R2',.R1 and R2 being hydrogen, alky-l,

aryl, etc., also *NHacylgroups which must be saponified' for the diazoti-sation, ,aromatically bound hydroxyl groups, radicals with the reactive methylene group-and the like. As known, the position of the reactivesubstituents in the arcmatic nuclei is decisive for thecapability of coupling with diazo compounds.- Beside this specific-substitutionof the radicals X1 and X2 also unspecific substituents come into. question, as far as they do not prevent the formation of azo dye?- tufis. 1 ,As examples maybe mentioned alkyl,

11 Claims. (01160- 143)- acylaminoy carboxyl, sulfonicacid groupsand so on. M

(b) Suitable organic radicals without diazo tisable substituents or without substituents enabling the azo coupling or being convertible into the same, such as, for instance radicals with the substituents NR1R2 (R1; meaning hydrogen or like RZ'QJKYI, aralkyl, aryl, acyl groups, radicals of heterocyclic ring systems etc.) OR (R representing hydrogen, alkyl, aralkyl, aryl groups and the like), I

cooH, -so3H and so forth. In this ca e it is,

of course, necessary that substituents of both the. first mentioned kinds, which. in themselves could enable the coupling with diazo components, stand in such positions, which prevent such a coupling.

. (c) Radicals of amino azo dyestufis which possibly may contain metallisable atom groupings.

((1) Inorganic radicals, like NH2, -OH, the hydroxyl group being introduced by hydrolytic exchange of a halogen atom of the cyanuric halide for their synthesis they can, beside the possibilities already illustrated above, still be after-treated in variousways in "substanceor on the fibre; thus,

especially the treatment with metal yielding agents, like copper,- chromiumsalts etc., may be mentioned. Moreover, it may be pointed out that surprisinglygthe dyeings made by means of the dyestuffs obtainable according to the present-in-'-.

yention are generally substantially improved-with regard to their waterand washing-fastness properties, when the same are after-treated with formaldehyde. I

The present invention; will nowbe illustrated by the following examples, wherein the partsare by weight. Of course,- the inventionis not 'tobe limited to the following-examples. i 1

Example 1 18.5 parts of cyanuric chloride are condensed at C; and in a neutral medium in form of a fine suspension with 40 parts of 4-nitro-4'- aminostilbene-2:'2-disulfonic acid. The primary condensation product is converted in the known manner 1 amino 4 hydroxybenzene-3-carboxylic acid into the tertiary condensation product The tertiary condensation product is then dissolved in 1200 parts of water and 140 parts of caustic soda lye at; 36 B. at 60-701C., where upon 180 parts of a grape-sugar solution of per cent strength are allowed to flow thereinto.

Then this mixture is maintained f or 2-3 hours, at 60-70 C.,'the base is neutralised by means of hydrochloric acid, precipitated with sodium chloride and finally isolated.

After having been dried, the dyestuiT con stitutes a'brown-orange powder, which dissolves in water with a yellow-orange coloration'fand dyes cellulosic, fibres in light-fast orange shades.

By an after-treatment with chromium salts,

brownish-orange shades of "considerably im-v proved 'waterand washing-fastness properties are obtained. By a simultaneous after-treatment with copper and chromium salts the fastness properties to water, towashing and to light are increased.

If the primary condensation product is reduced in the usual manner, a dyestuff is obtained which dyes cellulosic fibres in yellow-orang shades and whose waterand washing-fastness properties are improvedby a treatment with formaldehyde.

maple 2 The condensation: product from. 18.5 parts of cyanuric chloride, 4L0v parts of 4-nitro-4'-aminosti1bene-2:2'-disulfonic acid, 32 parts of dehydrothio-p-toluidine sulfonic acid and 17.3 "parts of metanilic acid is dissolved in 1500 parts of water and 100 parts ofcaustic soda lye of 36 B. at 60-70" Q. Then a solution of, 18 parts of glucose in200 parts of water are allowed to flow thereinto, whereupon the mixture is maintained for 2 hours at 60-70" C. Finally, the base is neutralised by means of hydrochloric acid, completely Example 3 V V "95 parts of the condensationproduct from 1 mol.- of cyanuric chloride, 1 mol. of 4-nitro4"- aminostilbene-2:2-disulfonic acid, -1 mol. of 1'-amino-4-hydroxybenzene 3 carboxylic acid and 1 mol. of dehydrothio p-toluidine "sulfonic acid are dissolved in'1200 parts of water and 100 parts of caustic soda lye of 36 B. at 70 C., whereupon 1'? parts of gluco'se'in' 200 parts of waterare allowed to' fiow thereinto. Then this mixture is maintained for 2 hours at' '70C., the base is neutralised'by means of hydrochloric acid, the dyestufi completely precipitated with sodium chloride and finally-isolated. i

The dried dyestuff constitutes a brown-orange by means of 30.6 parts of and! isolated, as soon as the reaction is complete,

powder, which dissolves in water with a yelloworange coloration and dyes cellulosic fibres in yellowish-orange shades. By an after-treatment with chromium or copper salts the waterand washing-fastness properties are increased.

Example 4 I 2-(4-hydroxy-3'-carboxyphenyl) -l:3 benztria- 201 and aniline is dissolved in 1200 parts of water and 100 parts of caustic soda lye of 36 B. at 60-70" C: Then 160 parts of a 10% grape-sugar solution are allowed to flow thereinto and the mixture is maintained for 3 hours at (SO-70 C., whereupon the dyestufi is isolated in the usual manner. i

The -dyestufi' constitutes, after having been dried, a brown-orange powder, which dissolves in:-water with a yellow-orange;coloration and dyes cellulosic fibres in light-'fas't reddish-yellow shades; By an after-treatment of the vdyeings with chromium or copper salts the fastness properties to water and to washing are increased.-

Example 5 Q The condensation product'from 18.5 parts of cyanuricchloride, 40 parts of/l-nitro-lf-aminostilbene-2:2-disulfonic acid and. '30; parts of 1 amino 4 acetaminobenzene is treated at 60-70" C. in 1800 parts of. waterandlOO parts of caustic soda lyeof 36 B. with, 160 parts of a 10% grape-sugar solution. The mixtureis kept for 3-4 hours at"60-70 0., thenthe dyestuff separated in the usual manner by means "of sodium chloride, isolated and, in, order to saponify.

the acetyl group, heated for instance for 1 hourwith 1200 parts of water and 150 parts of causetic soda lye of 36 B. to 95-100? C. Then the base is neutralised with hydrochloric acid, the dyestuiT is completely precipitated with sodium I chloride and filtered.

;The dried dyestuff constitutes a brown-orange powder dissolving in water with a yellow-orange coloration and dyeing cellulosic fibres in orange shades. The dyeings diazotised on the fibre and developed with l-phenyl-3-methyl-5-pyrazolone yield beautiful orange shades of a good water: and washing-fastness;

If after its reduction the. above described dyestuff is still treated in the known manner with a sodium hypochlorite' solution and subsequently saponified, a product is obtained yielding somewhat clearer dyeings. 1

Example 6, i

64.5 parts of the condensation product from 1 mol. of cyanuricchloride, 1 mol. of 4-mtro4'- aminostilbene 2:2 disulfonic acid, 1 mol. or 1 amino-4-hydroxy benzene-B-carboxylic acid and ammonia are dissolved in 1000 partsof water and parts of caustic soda'lye of 36 B. Then parts of a 10% grape-sugar solution are allowed to flow thereinto at 60-70 C., whereupon the mixture is worked up in the usual manner.

The dried dyestuff f orms fa brown-'orange'powder', which dissolves in'water with a yellow orange coloration and dyes cellulosic fibres in.

yellowish-orange shades, the waterand'wash ing-fastness properties of which can considerably be increased by a aft r-treatment with metal salts.

The reduction canalso be effectedby using Example 7 iThe condensation product from 18.5 parts of. cyanuric chloride, 40 parts of 4-nitro-lT-aminostilbene-2:2'-disulfonic acid and 54.2 parts of o-toluidine-methylene-o-cresotinic acid are dissolved in 1500 parts of water and 100 parts of caustic soda lye of 36 B., treated with 160 parts of a grape-sugar, solution at 60-70 C., then the mixture is maintained for 3 hours at this temperature and the interaction product separated in the usual manner is filtered off.

The dyestufi constitutes, when dried, a yelloworange powder dissolving in water with a yellow coloration and dyeing cellulosic fibres in yellow shades, which, when after-treated with chromium salts, possess very good iastness to water-and to washing.

Example 8 The condensation product, from l8.5 parts of cyanuric chloride, parts of 4-nitro-4'-amin0- stilbene-2:2'-disulfonic acid,.32 parts of dehydrothio-p-toluidine sulfonic acid and 14.3 parts of f1-ChlOIO-1 :3-diaminobenzene is dissolvedin 210 00- properties 1 parts of waterand 100, parts of caustic soda lye,

of 36 B. at -70 C., then parts o;f a 10% glucose solution are allowed toflow thereinto and the whole is maintained for Bhours at 60-70 C.; finally, the dyestufi' is separated in the usual manner and-isolated. v I The reddish-brown dyestuff dissolves in water with an orange-coloration and dyes cellulosic fibres in reddish-yellow shades, which, when developed with 1-phenyl 3-methyl-5-pyrazol-one,-

give clear, yellowish-orange shades of I good waterand washing-fastness properties.

The above reduction product can also be diazotised in substance and coupled for instance with 1-phenyl-3-methyl-5-pyrazolone or its substitu tion products. When working in this manner, yellow-orange dyestuffs are obtained which, when after-treated with formaldehyde, yield on cellulosic fibres dyeings which are distinguished by good water-and washing-fastness properties. Finally, it is also possible to -obtain dyestuffs having the same properties by first diaz-otising the condensation product described in this example, then coupling with pyrazolone derivatives and reducing the coupling products;

Example 9 82.5 parts of the condensation product from 1 mol. of cyanuric chloride, '1 mol. of 4-nitro-4'- aminostilbene-Z:2'-disulfonic acid, 1 mol. of 4- proved by an after-treatment with metal salts or formaldehyde Further; similar dyestuifs are' obtained; if in thisexample the anilineris replaced by lmonomethyl aniline, monoethyl aniline,.metanilic acid, m am-inobenzoic acid and the like. I

Example-.10

7a ,parts'of the condensation product. from 1 mol. of cyanuric chloride, 1 mol. of '4-nitro-4;

aminostilbene-2:2'-disulfonic acid, 1 mol. of 4- reddish-yellow shades, which, when after treated with formaldehyde possess very good fastness properties to water and to washing, Likewise the waterand washing-fastness are considerably. increased by an after-treatment with chromium salts, the shade becoming then somewhat greener and duller.

Example 11 3105 par-ts 0f the condensation product from 1 mol.-of cyanuric chloride, 1 mol. of 4-nitro-4'- aminostilbene z:2'-disulfonic acid, 1 mol. of 4- a-mi n-oAf-hy'droxy-Zi-carboxy 1 1-azobenzene and 1 mol. of dehydrothio-p-toluidine are redueedin 1200 parts ofv water and 100 parts of caustic soda lye of 36 B. at 60'-70 C. for 2-3. hours by means of parts of a 0% glucose solution and isolated inthe usual manner. 1

The dyestuff is a brown powder, which dis-s solves in water with a yellow-orange coloration and dyes cellulosic fibres in yellow shades, which, when after-treated with metal salts or formaldehyde, are distinguished by good ,fastness prop erties to washing and .Water.

' Exqrmple' 12 85 parts of the condensation product from 1 mol. of cyanuric chloride, 1 mol. of. 4-nitro-4'- aminostil'bene-2:Zf-disulfonic acid, 1 mol. of 4- amino-azobenzenei -slulfonic acid and aniline are dissolved in 1200 parts of water and parts of caustic soda lye of 36 B., then reduced within 3 hours at (SO-70 C. by means of 180 parts'of a 10% glucose solution and iso-' lated in the-usual manner.

'The dyestuffconstitutes abrown-orange powder, which dissolves-in water with an orange coloration and dyes cellulosic fibres in light-fast reddish-yellow shades by an after-treatment' with formaldehyde, are considerably improved with respect to their fastness properties A to water and-lto'washing.

Whenthe said dyestufi is after-treated with sodium hypochlorite, a product is obtained which 1 produces somewhatmore greenish-yellow shades;

4-hydroxyhenzene-3-carboxylic acid are reduced in the usual manner with glucose or'sodiumsul-. fide and isolated;

'I h'e' dyestuif constitutes a reddish-brown powder, which dissolves'in water with an orange col-- oration and dyes cellulosic fibres in yellow I shades, whoseiwaterand washing-fas'tness be-' comes considerably increased by an after-treat. mentwvith metalsalts. 1 I Y Edrample 14 The condensation product from 18.5 parts of cyanuric. chloride, 40 parts of 4-nitro-4'-aminostilbene-2:2-disulfonicacid, 62.1 parts of the dyestuif from diazotised p-toluene sulfo ester of the 1:8-aminonaphtho1-3zfi-disulfonic acid and 1-amino-2-methoxy-5-methylbenzene and aniline is dissolved in 1500 parts of water and 100 parts" of caustic soda lye of 36 B. at 40 C. then 160 arts of a 10% glucose solution are allowed to flow thereinto and this mixture is maintained for 2 hours at 35-40 C. For the complete saponification of the toluene sulfo ester the whole is still heated for 30 minutes up to 90-95 C.; after cooling the base is neutralised by means of hydrochloric acid, the dyestuff completely precipitated with sodium chloride and filtered ofi.

The reduction can also be carried out at 60- 70" C., the p-toluene sulfo ester being thus simulr taneously saponified. Finally, the p-toluene sulfo ester otthe condensation product may first also be saponified and then reduced; in this case the saponificatio-n can be carried out in an acid or alkaline reaction medium.

The dried dyestufi constitutes a red-brown powder, which dissolves in water with a yellowred coloration and dyes cellulosic fibres in light-j- I fast scarlet shades.

Example 16' 115 parts of the condensation product from 1 mol. of cyanuric chloride, 1 mol. of 4-nitro-4'-- aminostilbene-Z:2'-disulfonic acid, 1 mol. of amino-2-methyl-5-methox'y-1:1 '-azo benzene-4'- sulfonic acid and 1 mol. of 1-(4-aminobenzoyl) a m i n o-2-hydroxy-3-carboxybenzene-5-sulfonic I acid are reduced in the usual manner and isolated.

When dried, the dyestufi constitutes an ,orange powder; it dissolves in water with a yellow coloration and dyes cellulosic fib'res in yellow shades. By an after-treatment with chromium salts very good waterand washing-fastness are obtained, while scarcely changing the shades. 1

Example 17 92.6 parts of the condensation product from 1 mol. of cyanuric chloride, 1 mol. of 4-nitro-4'- aminostilbene-2:2' disulfonic acid, 1 mol. of 4- amino-Z-methoxy 2'-hydroxy 3-chloro -1:1'- aZobenzene-5'-sulfonic acid and aniline are-reduced in the usual manner and isolated.

' The dyestuff constitutes a brown powder, which dissolves in water with a yellow-orange colora tion and dyes cellulosic fibres in yellow-orange shades which, when after-treated with copper salts, give very light-fast, reddish-brown shades of good waterand washing-fastness properties.

If-"th'e above dyestufi is convertedinsubstance, e. g; by heating its aqueous solution for several hours with a solution of 25 parts of crystallised copper sulfate in 100 parts of water and 50 parts of concentrated ammonia, into the copper complex,there is obtained'a product dyeing cellulosic fibres in ver light-fast brown shades.

A similar dyestuff is obtained by replacing the abovedescribed condensation product by the condensation product from 18.5 parts of cyanuric chloride, 40 parts of ,4-nitro-4-aminostilbene 2:2-disulfo'nic acid and 35.8 parts of 4-amino-2- methoxy-2-hydroXy-3'-chloro-1 1. -azobenzene- 5'-sulfonic acid.

Example 18 The condensation product from 1 mol. of cya nuric chloride, 1mol.of 4-nitro-4'-aminostilbene- 2:2-disulfonic'acid, 1 mol. of 4-amino-4'-hydroxy-3-carboxy-1:1'-azobenzene and 1 mol. of 1:3-diaminobenzene-4-sulfonic acid is reduced and worked up in the usual manner.

' The dyestufi constitutes a brown powder, which dissolves in waterwith a yellow-orange colora-' tion and dyes cellulosic fibres in yellow shades. By diazotisation on the fibre and development with 1-phenyl-3-methyl-5-pyrazolone reddishyellow shades of good waterandwashing-fastness properties are obtained.

Example 19 I 88 parts of the condensation product from 1 mol. of cyanuric chloride, 1 mol. of 4-nitro-4'- aminostilbene-2-2-disulfonic acid, 1 mol. of 4- amin0-4'.-hydroXy 3-carboxy 1: 1'-az0benzene and 4-aminoaceta'nilide are reduced and worked up in theusual manner.

The brown-orange dyestufi dissolves in'water with an orange coloration and dyes cellulosic fibres in yellow shades. By an after-treatment with formaldehyde go'od-fastness properties to water and to washingare obtained.

If the above dyestufi is heated with diluted acid or withdiluted alkalis, the acetyl group is' split off. The saponified dyestufi gives on cellulosic fibres after diazotisation and development with 1-phenyl-3-methyl-5-pyrazolone, yellow:-.

orange shades of good waterand washing-fastness.

The same dyes'tuflf. is obtained, when in the above example the 4-,aminoacetanilide is replaced by 4-aminoformanilide.

Example 20 The condensation product from 18.5 parts of cyanuric chloride, 40 parts of 4-nitro-4-aminostilbene-2:2'-disulfonic acid, 25.7 parts 'of 4-,

amino- 4-hydroxy-3 carboxy 1:1-azobenzene and 32.2 parts of -amino-2-methyl 5-methoxy- 1:1'-azobenaene-4'-solfonic acid is reduced and worked up in the usual manner.

The dyestufi constitutes a red-brown powder? it dissolves in water with an orange coloration and dyes cellulosic fibres in yellow shades, which, when after-treated with formaldehyde, are distinguished by good waterand washing-fastness properties. The fastness properties to water and to washing can also be improved'by an aftertreatment with metal salts.

. Example 21 111 parts'of the condensation product from 1 'mol. of cyanuric chloride, 1 mol. of 4-nitro-4'- aminostilbene-2:2'-disulfonic acid, 1 mol. of the dyestufi obtainable from diazotised 4-arninoazobenzene-4'-sulfonic acid and 'aminonaphthol sulfonic'acid-2z5z7 and ,monomethyl aniline are dissolved in 1600'parts of water and 100 partsof caustic soda lye of 36 Be; then 1'70 parts of a 10 glucose solution'areallowedto flow thereinto at 35-40 C. andthe'whole is maintained at this temperature -for 2-3 hours. The dyestuff thus formed is worked up in the usual manner.

The dyestufi constitutes a violet-brown powder, dissolving in water witha red coloration and dyeing cellulosic fibres in good light-fast red shades, whose fastness properties to water and to washing can be improved byan after-treatment with formaldehyde. v v

Instead of monomethyl aniline, monoethyl-anilne may be used with the same result.

Example 22 The condensation product from 18.5 parts of cyanuric chloride, 40 parts of 4-nitro-4-aminostilbene-2:2-disulfonic acid, 23.9 parts of amino .naphthol sulfonic acid-2:5: 7 and 15.3 parts of 1-aminoa4-hydroxybenzene-3-carboxylic acid is waterand washing-fastness can be improved by The condensation product' from'-18i5yparts of cyanuric chlorideglO parts of 4- nitro-4'-aminostilbene-2:2' -disu1fonic acid and 35.8 parts of 2 (3' aminobenzoyl) -amino.-5-hydmxynaphtha- 1ene-7-sulfonic acid is reduced in the usual manner and the dyestufi isolated The dyestuff bein'g soluble in water with {a yellow-orange coloration dyes cellulos ic fibres in properties.

reddish-yellow shades which, when treated with p-nitrodiazobenzene, produce bright orange shades of "good water- If theabove dyestuffiscoupledin-an alkaline medium with diazotised anthranilic acid, a prodnot is obtained which dyes cellulosic fibres in orange shades. dyeings with copper salts beautiful brown shades of good fastness properties to light,to water and to washing are obtained.

A similar dyestuffisobtained byreplacingthe 2- (3-amin obenzoyl) -amino-5 hydroxynaphthalene-7-sulfonic acid by the 2-amino-5-h'ydroxy naphthalene-'T-sulfonic acid. i

In the following table further 'dyestuifs-obtain able according .to this invention are enumerated. In order to' simplify the .table only w-the" com ponents X1 and X2 of thexj'dyestufishaving the general formula C-N v v I I 'l I N=C 'soan soin soln S'OaH e X: X,

an after-treatment with formaldehyde. By an v wherein Z means an az o or azoxy bridge, are after-treatment with potassium chromate one ob indicated.

' Table D 1 1 Mezhod of aftteryemg on ce urea men X 1 losic fibres 7Me=n1etal salts I -F=iormaldehyde 1-amino-4-hydroxybenzene-3-carboxylicacid. Monomethylamine Yellow-orange"; 'F, "M Do Diethylamme... do E M Do Aniline. Do Monomethylamlme. M 1-amino-4-hydroxy-3-methy1benzcne-a-carboxylic acid Aniline o Sapomfled Dehydrothio-p-tolnidine suli'onic'acid l-gxmino -&hydroxy13ecarbpxybennene-5-sulonlc aci l-amino-4-hydroxy-3-carboxybenzene-5-sulfonicacid Aniline... 1-(3-aminobenzoyl)-amino-4-hydroxybenzene-3-car do boxylic acid. 3 5-amino-2-(4-hydroxy-3'-carb oxy-5-sulfophcny1)-l 23- do I benztriazol.

, Do 2 -(4-aminophenyl)-(naphtho -1- :2 :4z5-tnazol) 5': 7' -A disnlionic acid.

l ainino-4-liydroxybenZeneQ3-carboxylicacid mime...

and washing-iastness By an after-treatment of these Dehydi-othio-p-toluidine sulfonic acid 4-amino-5-methoxy-2-methyl-1 :1',-Bzob enzene-4-su1- Ionic acid. 5-amino-2-(2'-hydroxy-3-carboxy-5-suliophenyl) -1:3-

4-amino-2-acetyl-amino-4-chloro-1:1-azobenzene- 3"-sulionic acid. v Dchydrothio-p-toluidinesnlfonic acid Dimethylamine do Aniline Reddish-yellow F 4-amin0-5-methoxy-2-methyl-1 :1 -azob enzenedo 4-sulfonic'a'ci'd. I1- (3! -amino-benzoyl) -amino -4-hydr'oxybenzene-3-carboxylic"acid. 4-amino-5-methoxy-2-methyl-1:1-azobenzene- 4-sulioni'c acid. 1 4-amino-3-methoxy-h1 -azobenzene-3 -ca1-v boxylic acid. Aniline 4-amino 2 acetylramino-4-'ch1oro l:1-azoben menei'sulfonic acid. Dimethylamine Aniline' Do kamino z-methylw-wgsnlfoacetylamino-l:l-azoben- Dimethylamine. Ani1inc-.

6 amen o t z j Method of after x x V X 2 Dyeing on cellutreatment losic fibres Me =metal salts v v F =iorma1dehyde 4-am in0-2:5-dimeth0xy-1:1-azobenzene-4'-sulfonic Aniline Yellow-orange.-. F

ac 0 I Monomethylemine do F Do Dimethylamine F Dyestufl from diazotised p-toluene sulfo ester of the Ammonia F 1:8-aminonaphthol-3zfi-disulfonic acid and l-amino- 2-meth0xy-fi-methylbenzene, saponified.

7 D0 Diethylnmina do F DyestufE from cliazotlsed p-toluene sulfo ester of the Monomethylaniline' d 1:8-aminonaphthol-3:6-disulfonic acid and l-aminov r 2-methoxy-5-methylbenzene. Do 1 1-aminol-hydroxybenzene-3-carboxylic aciddo 'F, Me Do 1-(3-ammobenzoyl)-am1no-4-hydroxy-3-car- .do F, Me

o boxybenzene b-sulfonic acid. Dyestufi from diazotised p-toluene sulfo ester of the iline n; I R d n F 7 1:8-a1ninonaphthol-IizG-disulfonic acid and l-amino- 2:5-dimethoxybenzene, saponified.

1) Dimethylamine .do F Dn I 1-(4'-ammobenzoyl)-amino-4-hydroxybenzene do; F, Me

S-earboxylic acid.

e 1 Develo ed X 1 v V X 2 i v Diazotised and developed withdyeing on cellulosic fibres Del gdrothio-p toluidine-sulfonic 3-amin0acetanilide ;.r. Saponifimi" l-pheny1-3-methyl 5-pyra olone Orange 3-aminoformanilide do Do 4-aminoacetanilide. d0 4-amino-2-methyl-lzl -a.zobenzene-4- 3-aminoacetanilide do sulionic acid. v 4-emino-2;2v-dimethyl-1:l-azobend0 d0 Do,

zene-4-sulfonic acid. 1 p-Toluene m; ster: or the 1: 8- B-ammoformanlhde 1 .do fl-naph hol Red. aminonaphthol-3:fi-disulfonic acid V v diazotised and coupled with 1- amino-2-metl1oxy-5-methylbenzene. 1

D ,4-aminoformanilide 1- hen l-3-meth 1-5- 5Z0! n D zii-dianlfino--chjlojrobenzen fiapht hol .yfln ffnu f: l g lp red o -am no ormam l e 1- henyl-3-meth 1-5- azolone.. Diazotised 4-aminoazobenzene-4- 1:3-d1am1no-4-ehlorobenzen fl-fiaphthol. y pyr 1 1 12225? red sulionic acid V aminonaph e thol-sulionic acid 2:527. i

Do 1:3-d1ammoben zene-4-sulfonic acid Diazotised 4-aminoazobe'nzene 4-aminoformaml1de.

--- aminonaphtholsulfonic acid-2:517.

X 1 X Dyeing on cellu- Dyeing of the v losic fibres copper complex 2-amino l-hydroxybenzene-4-Su1 0nic acid Anil Brownish-ye11ow Yeuowbmwn m-anisidine.

Do; l-ammo-4-hydroxybenzene-3-carboxy1ic acid Do Dunethylamme Q-amino-l-hydroxybenzenei-sulfonic acid Anlline l-amino-2:5-dimethoxybenzene. 1 v

Do mm .ldo Do. Anthranilic acid 2-(3-a pepzoy Amlme Orange Yellow-brown.

amino-S-hydroxynaphthelene-7-sulion1c acid. I

Do 1-anqmo-2hydr0xy-B-cerboxybenzene-fi-sulronic mdo The metallisable dyestuffs mentioned in theamines and aromatic amines of the benzene above table can, of course, also be after-treated 55 series, theamines in both cases X1 and X2 being with metal salts on the fibre. b a I .ound with the ammo group to the cyanurlc rmg,

What we claim is: V V V 1. A process for the manufacture of dyestuffs Z stands for a member Selected m the group of the stilbene series of the generalformula consistingfof the azo and azoxy group's; which i i 5 tom SOaH t X2 r comprises condensing one mol. of a cyanuric wherein X1 stands fora member selected from halide with one mol. of 4-nitro-4'-aminostilbene the group consisting of radicals orf aromatic 7O amines of the benzene and naphthalene series -2:2"-disu1 fo'nic acid, one mol; of X1 H' and one mol; of Xz-H-zmd reducing the s'o-obtained condensation product in an alkaline medium with a smooth reducing agenpto fdrm1the'linkage v a argeszsan 2; A process forthe manufacture,of-dyestufis of the stilbene series/of the general rformula som s'ozn wherein X1 stands for a member selected from the group consisting of radicals of aromatic amines of the benzene and naphthalene series and of heterocyclic amines: of the thiazol and triazol series and Z stands for a member selected from the group consisting of the azo and azoxy groups, X, being bound with the amino group to the cyanuric ring which comprises condensing one mol. of a cyanuric halide with one mol. of 4- nitro-4'-aminostilbene-2:2'-disu1fonic acid, one

mol. 0t X1-H and one mol. of aniline and reducing the so-olotained condensation product in an alkaline medium with a smooth reducing agent to form the linkage Z.

3; A process for the manufacture of dyestuffs of the stilbene series of the general formula wherein Z stands lfor a member selected from the group consisting of the azo and azoxy groups and the: benzene nuclei A: containing substituwherein Z stands for a member selected from the group consisting of the azo and azoxy groups and the benzene nuclei A containing substituents, at least one of them imparting'solubility in vwater, which comprises condensing one mol. of

cyanuri'c halide with one mol. of 4-nitro-4'- aminosti1bene-2:2-disulfonic acid, one mol. of a 5- amino-2.phenyl-l 3#benztriazol derivative and one mol. of aniline and reducing the so-obtairred condensation product in an alkaline medium with a smooth reducing agent to=form the' link- .entaatleastQneof .them i'mparting solub-ilityin "a'ge -Z g 7 MM;

water, which comprises *conden sing "one-mol. of cyanuric halide with one mol. of 4.-DitrO+-4I!-al'ni 5. A processfor the manufacture of zthe-s til bene-2:2 '-disu1fonic acid, one "mol. of 4aminobene dyestufi of theformula r 4' -hydr0xy-'1 1-azoloenzene-3'--ca.rboxylic 1 acid which Comprises condensing one mol. of cyanuric chloride with one mol. of 4-nitro-4 aminostil- I e bene-2:2-disulfonic acid, one mol. of 4-aminoand one mOL'Of aniline and reducing the so-ob- 1:1-azobenzene-4'esulfonic acid and one mol. of t ained condensation product in an alkaline meaniline and reducing the so-obtained 00116181188: dium Witha smooth reducing agent. tion product in an alkaline medium with a smooth 7. A process for the manufacture of the stilreducing agent. bene dyestufi or the formula e w r OCOOH 6. A process for the manufacture of the stilwhich comprises'condensing one mol. of cyanuric bene dyestufi of the formula chloride with one mol. of 4;-nitro-4'-aminostilc v so H s03]: 8on1 o I a 'which'comprises condensing one molrof cyanuric bene- 2;2'-disulfonic acid, on mol. of 5-amj chloride with one mol. of 4-nitro-4'-aminostil- 2 -(4'rhydroxy-3r-carboxy) -pheny1-.-1:3-benztriazol'and'onei mol. of anilinerand reducing the "so obtained condensationproduot in an alkaline medium with asmooth'reducingagent. j l

8. The dyestufis of the stilbene series of the eneral formula wherein each X1 stands for the same member selected from the group consisting of radicals of aromatic amines of the benzene and naphthalene series and of heterocycli c amines of the SOIH thiazol and triazol series, each X2 stands for the same member selected from the group consisting of hydroxy and amino groups and radicals of low molecular aliphatic amines and aromatic COOH amines of the benzene series, the amines ln-both cases-12x1 :and X2 beingbound with the amino v group to the cyanuric ring,- Z' stands for a mem ber selected from the group consisting pi the azo and azoxy groups, being orange to powders dyeing cellulose fibres in yellow to red shades. 9. The dyestufi of the stilbene series of the formula s on; S 0:11

l -NH I NEE- 

